Washing composition containing suds suppressing agents

ABSTRACT

Washing compositions useful in automatic washing machines comprising conventional detergent compounds and additives and a suds suppressing piperazine derivative wherein the alkyl groups have 9-21 carbon atoms.

WASHING COMPOSITION CONTAINING SUDS SUPPRESSING AGENTS Inventors: Kurt Kosswig; Herbert Meister,

both of Marl, Germany Assignee: Chemische Werke Huls Aktiengesellschaft, Marl, Germany Filed: Sept. 28, 1973 Appl. No.: 401,691

Foreign Application Priority Data Dec. 23, 1975 [56] References Cited UNITED STATES PATENTS 2,383,525 8/1945 Tucker 252/542 2,421,707 6/1947 Malkemus 260/268 C 2,868,791 l/l959 Steele 260/268 C 3,422,020 l/l969 Schmadel et al. 252/99 3,547,932 12/1970 Gerecht 252/542 X 3,600,320 8/l97l Schmadel et al. 252/542 X Primary Examiner-Thomas J. Herbert, Jr. Attorney, Agent, or FirmMillen, Raptes & White 57 ABSTRACT Washing compositions useful in automatic washing machines comprising conventional detergent compounds and additives and a suds suppressing piperazine derivative wherein the alkyl groups have 9-21 carbon atoms.

8 Claims, No Drawings WASHING COMPOSITION CONTAINING SUDS SUPPRESSING AGENTS BACKGROUND OF THE INVENTION This invention relates to washing compositions containing piperazine derivatives as foam controlling or suds suppressing agents. Washing compositions which produce excessive suds are undesirable for use in modem drum-type washing machines. Desirably, washing compositions for use in automatic washing machines are those which initially exhibit a relatively good suds formation in the washing liquor at a low temperature (up to about 50 C-60 C) but tend to become low in suds during subsequent transition toward higher washing temperatures. Excessive sudsing or foaming is desirably avoided to prevent overflow of suds out of the washing machine.

Suds suppressing additives are added to washing compositions which are effective predominantly at temperatures higher than 60 C. Thus, this is the case with strongly foaming or sudsing anionic washingcompositions of the sulfate and/or sulfonate types, or in the case of the salts of the carboxylated alkyl polyglycol ethers of the general formula, R(OCH CH O[CH COOH, wherein R is C H to C H n is to 20, and m is I to 4.

A number of substances are known which can be added to washing compositions as foam or suds suppressors. Thus, it is conventional to use soaps of saturated fatty acids (DOS [German Unexamined Published Application] 2,015,435), nonionic highly molecular ethers, and esters of the ethylene oxide and propylene oxide condesation products of alcohols. Disadvantages of these substances are that they are not universally applicable in washing compositions and that they do not exhibit sufficient defoaming or desudsing action as in the case of dodecyl sulfaonates and alkyl sulfates.

Furthemiore, diurethanes are also known as foam suppressors (DOS 2,043,086). In these diurethanes, the optimum desudsing effect, at various temperature ranges, depends on the chain length. The diurethanes with chain lengths of -14 carbon atoms develop their optimum effect at -60 C., while those with chain lengths of 18-22 carbon atoms at 60-100 C. A disadvantage of the diurethanes is that isocyanates are necessary as the basic raw material, which, in turn, must be produced from amines or diamines, Long-chain amines, such as octylamine, laurylamine, or stearylamine, must be produced by a cumbersome process which involves reacting the corresponding chlorides with ammonia, or by the hydrogenation of the acid nitriles, and the reaction of the amines with the isocya nates requires even an additional, more expensive reaction step.

Triazine derivatives are also known (DAS [German Published Application] l,257,338) as foam suppressors of a broader, universal application spectrum, which are independent of the chemical constitution of the washing composition. They are produced by reacting cyanuric chloride with alkyl amines, wherein again long-chain amines are used, which in the nonnal case must be manufactured in two stages from the corresponding alcohols via the chlorides, or from the acids via the nitriles. Furthermore, hydrogen chloride is formed during the reaction, which is bound with equimolar amounts of amine. The amine consumed for binding the hydrogen chloride must first be regenerated from the salt before being reused. Therefore, the production of the triazine derivatives is cumbersome and expensive.

In accordance with the present invention a low sudsing washing composition containing a foam or suds suppressing agent has now been discovered which can be manufactured simply, inexpensively, and in high yields, which has an excellent foam controlling ability, and furthermore which can be used universally.

OBJECTS OF THE INVENTION Accordingly, it is an object of this invention to provide an improved washing composition characterized by controlled foaming during use in automatic washing machines.

Another object of this invention is to provide a low sudsing washing composition containing a suds-suppressing agent comprising piperazine derivatives produced by simple, inexpensive, and conventional processes.

Upon further study of the specification and appended claims, further objects and advantages of this invention will become apparent to those skilled in the art.

SUMMARY OF THE INVENTION Briefly the above objects and other objects are attained by the present invention by providing a washing and cleaning composition containing usual detergents and additives, and which is characterized in that it contains piperazine derivatives of the formula:

0 0 ll I R,-c-N N-C-R2 wherein R, and R are alkyl groups of 9-21 carbon atoms, as the desudsing or defoaming agents.

DETAILED DESCRIPTION OF THE INVENTION The piperazine derivatives of the present invention are insoluble or of low solubility in water, depending on the length of the acyl residue. The desudsing or defoaming effect is only moderately strong at temperatures between 2040 C., but becomes stronger at 60 C., and reaches the optimum effect at C. and there- 3 above. The '..'ashing compositions of this invention possess especially favorable properties if the chain length of the alkyl groups of the piperazine derivatives is 1 1-19 carbon atoms. The defoaming effect decreases with a reduced number of carbon atoms in the residue R, especially at a high temperature, and is hardly noticeable in the case of carbon atom numbers of below 7 in the residue R. The use of piperazine derivatives of more than 19 carbon atoms, i.e., up to 21 carbon atoms, in the residue R is not as suitable from an economical viewpoint. The higher fatty acids (e.g., behenic acid, lignoceric acid) required for the production of such piperazine derivatives are not as easy to produce, in contrast to lauric, myristic, palmitic, and stearic acids, which, when reacted with piperazine, result in excellent desudsing agents. The alkyl groups can also contain branches and double bonds, but piperazine derivatives of such chain configurations do not offer any particular desudsing advantages from a laundering standpoint as compared to the piperazine derivatives with straight chains.

The quantity of piperazine derivatives added to the washing compositions is 1-40% by weight, preferably 520% by weight, based on the detergents in the washing compositions. When adding less than 1%, practically no desudsing action can be observed; at above 40%, no increase in the desudsing action is particularly rioticeable. The quantity of piperazine derivatives added to the washing compositions is 0.1 12% by weight, preferably 0.5 6 by weight, based on the total weight of the washing composition.

- The washing and cleaning compositions can additionally contain the conventional additives, such as phosphates, silicates, carbonates, borates, cellulose derivatives, etc.

The piperazine derivatives of the invention can be produced in accordance with conventional methods, most simply and inexpensively by splitting off water from piperazine and fatty acids containing the desired R residue. The reaction is particularly simple if the reactants are refluxed in a water-insoluble solvent of an appropriate boiling point, wherein the water is removed from the cycle. Suitable fatty acids are straightchain, native fatty acids, synthetic fatty acids having an even or odd number of carbon atoms, and with straight or branched chains. The advantages attainable by the desudsing agents of this invention reside particularly in that they are readily producible technically; that they deploy the optimum of their effectiveness at about 60 C. and thereabove; and that the foam level in the washing machines can be regulated by controlled dosages. As demonstrated in the subsequent example, they are superior to the conventional desudsing agents with respect to their desudsing action.

Die foam or suds suppression set forth in the examples was measured in accordance with three different methods:

a. Air injection method according to Merrill and Moffett (Oil and Soap 21, 170 [1944]). In the Merrill and Moffett method, the foam is produced by air injection. The apparatus consists of a column having a height of 40 cm. and an inside diameter of 9 cm., equipped with a heating jacket. At the bottom, the column has an installed porous glass plate 4 having a diameter of 3 cm. 400 cc. of the test solution is introduced into the column. A marker in the form of a constriction of the column is provided 25 cm. above the level of the liquid. Air at an excess pressure of 20 cm. H O column is introduced into the test solution through the glass frit, and the time is measured within which the thus-formed foam has reached the marker. The longer the duration of this time (i.e., the lower the sudsing ability of the substance), the better if the effect of a desudsing additive. In case of an especially strong desudsing action, the foam or suds does not reach the marker at all; in this case, the attained suds level is indicated. Examples 1-6 were measured in accordance with the method of Merrill and Moffett. The values set forth therein are averages from five measurements.

b. Foam spraying method according to DAS 1,257,338. In the foam spraying method, the suds are generated by spraying the test solution. The device, utilized in a compact design, consists of a cylindrical vessel of stainless steel having a height of cm. and an inside diameter of 26 cm. The liquid provided in the device is recirculated by a pump and sprayed from an annular pipe arranged at the top of the vessel, which pipe has numerous small openings directed downwardly. Upon impingement on the liquid below the pipe (falling height 50 cm.), suds are formed, the level of which is measured after specific times. The lower the suds level, the higher the defoaming or desudsing effect. Examples 7 and 8 were measured according to the foam spraying method.

c. Foam beating method according to DIN 53 902. in this method, the volume of the foam or suds is measured.

This procedure was employed in Example 9.

In the following examples references to German Hardness (dH) of water is defined as follows: 1 German hardness 0.357 milligram equivalents/liter of calcium ions, or 17.8 ppm. of CaCO EXAMPLE 1 2 g. of a 50% by weight sodium dodecylbenzenesulfonate solution was dissolved in 1 liter of drinking water having a hardness of 12 dH. Then, varying amounts (0.1 g. and 0.4 g., respectively) of the desudsing agent (defoaming additive) were added to this solution. The foam or suds characteristic is tested in the apparatus according to Merrill and Mofiett. The results are compiled in Table 1. it can be seen therefrom that the piperazine derivatives of this invention are superior to the defoaming or desudsing substances of the prior art in their desudsing effect.

EXAMPLE 2 In this example, the defoaming or desudsing effect of the piperazine derivatives of this invention is demonstrated in soft water and in hard water. For this purpose, 1 g. of dodecylbenzenesulfonate was dissolved in distilled water (0 dH) and in drinking water 12 dH), respectively, and the foam or suds is measured with and without the addition of a defoaming additive. The results are compiled in Table 2.

TABLE 1 Example Defoaming Additive Temperature 20 C. 40 C. 60 C. 80 C.

I Without additive 272 sec. 242 sec. 205 sec. I48 sec.

0.1 g. Dilauroylpiperazine 390 sec. 370 sec. 480 sec. Foam level 20 cm. 0.! g. Trilaurylamino-s-triazine 360 sec. 325 sec. 360 sec. Foam level for comparison 20 cm. 0.4 g. Dilauroylpiperazine 420 sec. Foam level Foam level lO cm. 2-3 cm. 0.4 g. Trilaurylamino-s-triazine 300 sec. 270 sec. Foam level for comparison cm. (H g. Dipalmitoylpiperazine 390 see. 3l0 sec. Foam level Foam level cm. 6 cm. 0.] g. Distearoylpiperazinc 360 sec. 300 sec. 300 sec. Foam level 5 cm. 0.4 g. Distearoylpiperazine 300 sec. 300 sec. Foam level Foam level 10 cm. 5 cm. 0.4 g. Tristearylamino-s-triazine 305 sec. 340 sec. Foam level Foam level for comparison I cm. 8 cm. 0.] g. Mixture l:l of dipalmitoyL 330 sec. 3 l0 sec. 280 sec. 480 sec.

and distearoylpipcrazine 0.4 g. Dicaproylpipcrazine 280 sec. 270 see. 250 sec. I85 sec.

for comparison EXAMPLE 3 )4 Carboxymethylated alkyl polyethylene glycol 1.0 g. of olefin sulfonate (C -C was dissolved in l 25 1 cl as [:8 sodiulrlnlsulltl I liter of distilled water (O dH) or dnnkmg water (12 3 fg f gg 'ffi g fij me dl-l) and measured with and without the addition of 2 7 sodium silicate defoaming substances, as described in Example 1. The 8 Z: e l s are Compiled m ab 2 20 '71 sodium perhorate with 4 moles of water of crystallization EXAMPLE 4 0.2 optical brightener.

2.0 g. of alkane sulfonate (C -C was dissolved in 1 liter of distilled water (0 dH) and drinking water (12 dH), respectively, and measured as in Example 1 with or without adding distearoylpiperazine. The re- To this solution, 0.4 g. of the defoaming additive was added. The foaming behavior is tested in the apparatus according to Merrill and Moffett. The results are com- Sults are set f h i T bl 2 piled in Table 3. It was found that, in a finished detergent formulation, the piperazme derivative of this In EXAMPLE 5 vention has superior properties, in that it ensures a 4 ofa washmg agent f h f ll i composition uniform foam level In the entire temperature range. was dissolved in 1 liter of water:

TABLE 2 Ex- Defoaming Additive Water Temperature ample Hardness 20 C. 40 C. C. 80 C.

2 Without additive 0 dH 325 sec. 3 l0 sec. 290 sec. 2l0 sec. l2 dH 272 sec. 242 sec. 205 sec. 148 sec. 0.4 g. Dilauroylpiperazine 0 dH 370 sec. 340 sec. 390 sec. Foam level 20 cm. l2 dH 420 sec. Foam level Foam level Foam level 0 cm.

l0 cm. 3 cm. 0.4 g. Dipalmitoylpiperazine 0 dH 450 sec. 390 sec. Foam level Foam level l0 cm. 0 cm. l2 dH 390 sec. 330 sec. Foam level Foam level 15 cm. 6 cm. 0.4 g. Distearoylpiperazine 0 dH 330 sec. 330 sec. 450 sec. Foam level l2 cm.

12 dH 300 sec. 300 sec. Foam level Foam level 5 cm.

l0 cm. 0.4 g. Tripalmitylamino-s- 0 dH 340 sec. 350 see. Foam level Foam level triazine for comparison l5 cm. l4 cm.

l2 dH 320 sec. 300 sec. Foam level Foam level I I cm. l2 cm. 0.4 g. Tristcarylamino-s- 0 dH 3 l0 sec. 3l0 sec. 360 sec. 300 sec.

triazine for comparison l2 dH 305 sec. 340 sec. Foam level Foam level I em. 8 cm. 3 Without additive 0 dH 290 sec. 265 sec. 220 sec. I60 sec. l2 dH 295 sec. 255 sec. 225 sec. I see. 0.4 g. Dilauroylpiperazine 0 dH 290 sec. 270 sec. 230 sec. 200 sec.

12 dH 290 sec. 260 sec. 250 sec. Foam level l5 cm. 0.4 g. Trilaurylamino-s- 0 dH 290 sec. 265 sec. 230 sec. I see.

triazine for comparison l2 dH 295 sec. 260 sec. 230 see. Foam level 20 cm. 4 Without additive 0 dH 440 sec. 450 sec. 510 sec. 530 sec.

' 12 dH 3 l0 sec. 290 sec. 270 sec. 2H) sec. 0.4 g. Distearoylpiperazine 0 dH 330 sec. 330 sec. 540 sec. Foam level 5 cm.

12 dH 300 sec. 290 sec. Foam level Foam level 20 cm. l8 em.

the time for reaching a certain foam level at about 300 EXAMPLE 6 1.0 g. of dodecylbenzenesulfonate, 2.0 g. of sodium triphosphate, and 2.0 g. of sodium silicate were dissolved in 1 liter of distilled water dH) or drinking water 12 dH) and measured as set forth in Example 1 with and without the addition of dilauroylpiperazine. The results are set forth in Table 3. The example TABLE 3 Ex- Defoaming Additive Water Temperature ample Hardness C. C. 6 80 C.

5 Without additive 12 dH 290 sec. 280 sec. 280 sec. .220 sec. 0.4 g. Dilaumylpiperazine 12 dB 290 sec. 280 sec. 280 sec. 285 see. 0.4 g. Trilaurylamino-striazine for comparison 12 dH 300 sec. 300 sec. 300 sec. 260 sec. 6 Without additive 0 dH 305 sec. 26$.sec. 225 sec. 170 sec. 12 dH 295 sec. 260 sec. 225 sec. 170 sec. 0.4 g. Dilauroylpiperazine 0 dH 295 sec. 275 sec. 290 sec. 3 30 sec. 12 dH 290 sec. 310 see. I 280 sec. 300 sec.

TABLE 4 Ex- Defoaming Additive 40 C. 60 C. 80 C. ample Foam Level in cm. After Foam Level in em. After Foam Level in cm. After 0.5min 1min 3min 0.5min 1min 3min 0.5min 1min 3min 7 Without additive max. max. max. max. max. max. max. max. max. (cm) (50cm) (50cm) (50cm) (50cm) (50cm) (50cm) (50cm) (SOcmJ 0.1 g. Dilauroylpiper- 14.0cm 13.5cm 13.3cm 295cm 26.8cm l4'.5cm 42.0cm 400cm 37.5cm

azme 0.3 9. Dilauroylpiper- 3.0cm 1.8cm 1.5cm 3.8cm 3.2cm 3.0cm 6.5cm 4.5cm 0.5cm

uzinc 0.5 g. Dilauroylpipcn 10cm Locm 1.0cm 2.1cm 1.6cm 1.1cm 1.9 cm 0.4cm 0.30m

uztnc 0.3 g. Trilaurylamino-smax. max. max. max. max. max. max. max. max. triazine for (50cm) (50 cm) (50cm) (50cm) (50cm) (50cm) (50cm) (50cm) (50cm) comparison (1.5 g. Trilaurylamino-striazine for 7.6cm 7.3cm 7.2cm 5.0cm 4.0cm 2.5cm 4.5cm 2.5cm l 2cm comparison 1t Without additive max. max. max. max. max. max. (50cm) (50cm) (50cm) (50cm) (50cm) (50cm) 0.3 g. Distearoylpiper- 35cm 32cm 28cm 16cm 1 1cm 17cm azine 0.3 g. Behenic acid sodium salt for 48cm 47cm 46cm 47cm 47cm 45cm comparison shows that the substance of this invention, when EXAMPLE 9 further electrolytes are added, has a foam-regulating effect in the range from 20 to 80C., by maintaining seconds, independently of the hardness of the water.

EXAMPLE 7 foam spraying apparatus according to DAS 1,257,338.

The pH of the solution is set to 9.5; the solution was recirculated by a pump at a rate of 465 liters/minute. The results are set forth in Table 4.

EXAMPLE 8 1.0 g. of the sodium salt of a carboxymethylated alcohol oxyethylate, the alcohol residue of which consists of a mixture of dodecanol and tetradecanol and 1.0 g. of olefin sulfonate was dissolved in 1 liter of water of 0 dH or 12 dH and tested with and without a defoaming agent in accordance with the manual beating method, DIN 53,902 (20 beats in 20 seconds). The thus-obtained amount of foam (in cm) is a measure for the defoaming action. The results are compiled in Table 5.

The preceding examples can be repeated with similar success by substituting the generically or specifically described reactants and/or operating conditions of this invention for those used in the preceding examples.

From the foregoing description, one skilled in the art can easily ascertain the essential characteristics of this invention, and without departing from the spirit and scope thereof, can make various changes and modifications of the invention to adapt it to various usages and conditions.

TABLE 5 Ex- Defoaming Water 40 c. 60 c. c. ample Additive Hardness Amount of Foam After Amount of Foam After Amount of Foam After 0.5min 1min 3min 0.5min 1min 3min 0.5min 1min 3min 9 Without 0 dH 510cm" 505cm 470cm 550cm 540cm 510cm 570cm 550cm" 495cm additive 12 dH 370cm" 350cm 330cm 450cm 430cm" 410cm 460cm" 450cm 410cm" 0.] g. Distcaroyl- 0 dH 280cm" 270cm 250cm" 280cm 270cm 210cm 280cm 225cm cm" piperazine 12 dH 210cm 205cm 180cm" 200cm 170cm cm 205cm" 165cm" 140cm TABLE 5-continued Ex- Defoaming Water 40 C. 60 C. C P e Additive Hardness Amount of Foam After Amount of Foam After Amount of Foam After 0.5min lmin 3min 05min lmin 3min 0.5mm lmm 3mm 0.1 g. Trilauryl- 0 dH 430cm 405cm 370cm 490cm 400cm" 370cm 405cm" 390cm 340cm amino-striazine for com- 12 dl-l 360cm 350cm 345cm 330cm 295cm 260cm 340cm 280cm 225cm" arison 5.3 g. Distearoyl- 0 dH 150mm lZScrn" l20cm" l70cm" 155cm 130cm" 180cm" l cm 50cm" piperazine l2 dH 75cm 75cm 70cm" 100cm 90cm" 85cm llOcm 95cm 85cm 0.3 g. Trilauryl- 0 dH 230cm 225cm 2l0cm' 245cm 225cm 210cm 250cm 200cm 170cm umino-striazine for l2 dH 2l5cm ZIOcm l85cm 230cm 225cm" l'95cm 275cm 250cm 215cm comparison What is claimed is:

l. A low-sudsing washing composition comprising detergent compounds and additives, and l40% by weight, based on the weight of the active detergent compounds of the washing composition, of a suds-suppressing agent, said agent being a piperazine derivative of the formula:

wherein R and R each are alkyl groups of 9-21 carbon atoms.

6. The washing composition of claim 1 wherein the agent is dipalmitoylpiperazine.

7. The washing composition of claim 1 wherein said agent is 0.1-l2% by weight of the total composition.

8. The washing composition of claim 2 wherein said agent is O.56% by weight of the total composition. 

1. A LOW-SUDSING WASING COMPOSITION COMPRISING DETERGENT COMPOUNDS AND ADDITIVES, AND 1-40% BY WEIGHT, BASED ON THE WEIGHT OF THE ACTIVE DETERGENT COMPOUNDS OF THE WASHING COMPOSITION, OF A SUDS-SUPPRESSING AGENT, SAID AGENT BEING A PIPERAZINE DERIVATIVE OF THE FORMULA:
 2. The washing composition of claim 1 wherein said agent is present in amounts of 5-20% by weight, based on the weight of the active detergent compounds of the washing composition.
 3. The washing composition of claim 1 wherein R1 and R2 each are alkyl groups of 11-19 carbon atoms.
 4. The washing composition of claim 1 wherein the agent is distearoylpiperazine.
 5. The washing composition of claim 1 wherein the agent is dilauroylpiperazine.
 6. The washing composition of claim 1 wherein the agent is dipalmitoylpiperazine.
 7. The washing composition of claim 1 wherein said agent is 0.1-12% by weight of the total composition.
 8. The washing composition of claim 2 wherein said agent is 0.5-6% by weight of the total composition. 